Condensation product and method of preparing and using same



Patented Nov. 26, 1946' UNIT-Bo;

, STATES FF Ef @CONDENSATION rItoDUcrrANnMETHoDoF II PREPARING'AND-USING I Eugene Lieber, New York, N. 56., and Marvin E.- l

Thorner, Corpus Christi, Tex., assignors to Standard 'Oil Development Company, a corporation of Delaware'- No Drawing, Original application November'15, 194:1, Serial N0. 419,314. Divided and thiSB/llplication September 15, 1944, Serial No. 554,344

to Y use relatively long: chain. or o -high "molecular,

weight aliphaticicompounds, such as chlorinated paraffin wax' or corresponding olefiris," for such condensation: 1 i .I j One object of thepresent invention isrto. avoid the use of suchlong-chain. aliphatic compounds, and another object is to ruse aliphatic compounds which are saturated in respect to hydrogen (i. e., I free from olefinic linkages) and yet do not contain any reactive halogen atoms as are present in chlorinated paraffin wax. I

Broadly, the invention comprises the production of condensation products having wax-modi fying properties, by' chemically condensing a I lower saturated aliphatic ether with-" an'aromat'ic 2'5 cially onewhich'is a good solvent for the resultcompound. This condensationis preferably car ried out by the use of a Friedel-Crafts catalyst 1 used for according to the procedure commonly effecting such condensations. I- II The lower saturated aliphatic ether to beused is one having a low molecular weight and a low number of carbon atoms. Although some modified ethers may be used, it is preferred to use ethers having the general'formula R'-O'R,

where R and R are like or unlike alkyl groups and where the total number of carbon atoms in R and R. together is less than 10, and preferably less than '7 carbon atoms. such ethers include dimethyl ether, di-ethyl ether, dipropyl ether, di-isopropyl ether, di-sec- I ondary butyl ether, methyl isopropyl ether, isopropyl tertiary butyl ether, etc, or mixtures of two or more such pure compounds, or commercial products of which such ethers represent the contain at least two replaceablehydrogen, atoms,

on the nucleus, or, in other words, so long as they Specific examples of 7 (Cl 252.52)' I I are still subject to Friedel-Crafts condensation. Specific examples of suitable aromatic compounds include benzene, naphthalenaanthracene, phenanthrene, toluene, xylene, amyl ben zene, retene,qphenol,- alphaor beta-naphthol, cresol, anisole, tertiary'amyl phenol, diphenyl, and *diphenyl oxide. The Friedel-Crafts'catalyst to be used ineffecting; this condensation of, the loweraliphatic I 10 ether with :thev aromatic compound, accordingto this. invention, is preferably anhydrous, aluminum chloride, although otherjFr iedel-Crafts catalysts can be, used, such as boron-fluoride, ferric chlo-v I ride, titanium: tetrachloride',- boron trichloride, antimony chloride,fzinc chloride, .landin some ceses'seyenhydrogen fluoride; 1 3 The proportions 'of reactants to be usedshould be about to-5;mols, preferably to 215111015, of lower aliphatic ether to 1 mol of aromatic zo compound and the amount ofcatalyst should be,

for instance in the case of aluminum chloride,

about to 4 mols-preferably 1-3 mols per mol o a ic com oun The use of an inert diluent or solvent,1espeing high molecular weight condensation product, "is optional but is preferred, and if used,"should 3O catalyst; I

,..In carrying out the invention," the operating conditions to be used should include a tempera- 'ture between the approximate limits of room temperature and 300" F., preferably mixing the reactants and catalyst at about room temperature and then after any initial reaction has begun to subside, heating the reaction mixture to a final temperature of about 150-250 F., with a reaction time of about to 10;.hours, usually about 1 40 to 5 hours. The .reactants and catalystcan be mixed in any desired order, for instance,- the aliphatic ether and the aromatic compound can be mixed together first, with or without solvent, and then ,the catalyst added, or the catalyst may be mixed with the aromatic compound, and then the aliphaticether subsequently added.

After the reactants and catalyst have been mixed together and after the reaction mixture has been heated to the desired final temperature 0 fora sufiicient time to complete the reaction, the "reaction mixture. is, then cooled, diluted with a convenient volume of kerosene, light chlorinated hydrocarbon or other suitable diluent, e;-v tralized by any of the methods familiar to the firiedelqrafts art, 1, e.,. by adding water, alcohol,

be present about /2 to 10 volumes, preferably. I f1-5 volumes, per volume of total reactants, and;

dilute aqueous caustic soda solution, etc., a mixture of alcohol and water being very suitable. The reaction mixture is then separated, as by settling, into two layers, the aqueous layer con- 4 are tested in a 2% or 5% concentration in a waxy mineral lubricating oil base stock having a pour point of +30 F.

" Example 1 taining the aluminous sludge being removed, {and 5 j .v 1 k H v the kerosene extract, after washing with water, is Into a 3-liter-4-neck round bottom flask fitted then distilled under reduced pressure, i. e., with. with a mechanical stirrer, reflux condenser, therfire and steam or with vacuum (e. g. 5-50 mm, mometer and d pp g funnel were Placed 130 mercury at absolute pressure) to a temperature g aInS of di-sec. butyl ether, 128 of naphthalene of about 500 or 600 F. to remove solvent and and 500 cc. of kerosene (heavily treated with sullow-boiling products The distillation. residue furic acid before use) as solvent. Means were constitutes the desired condensationproduct of provided for cooling and heating the reaction this invention. flask. The mechanical stirrer was started and This product generally has a consistency rangwhile maintaining a temperature of 60 F., 300 g. ing from a viscous oil to a hard resin and has a of anhydrous A1C13 were slowly added to the recolor ranging from green to brown or black. This action mixture over a period of 45 minutes. After product is soluble in mineral oils, has a fairly the addition of the A1013 the reaction mixture was high molecular weight, e. g., about 500 to 2,000, heated to 150 F., and maintained thereat for 4 and has the property of modifying the crystal hours, after which time it was diluted with a fur- Structure of Waxes Such as paramn wax h ther quantity of kerosene, cooled to 100 F., and added to compositions containing such wax. For the h destroyed y Slowly adding 500 instance, when about 0.510.0%, preferably about Water After Settling, the kerosene eXtI'act was 1-5%, of this wax modifier is added to a waxy Washed free of acid and then distilled with fire lubricating oil, such as a Pennsylvania or other and steam to F: in Order to remove Solvent paraifinic type lubricating oil having a relatively a low-boiling p o u t bOtt m es due 60mhigh pour point, the resultant blendwill have a prising I14? of a green viscous oil was obsubstantially lower pour point; this condensation mined as p This Was found 110 be freely product is therefore an effective pour depressor soluble. in.lubricating-oil in a l p P for'waxy oils. A small amount of this wax modi- 'When 2% of this condensation p uct Wa fier is also useful as a dewaxing aid for removing added to a y Oil/the P011 Point Of Which Wa wax from mineral lubricating oils of undesirably +.30 the pour pointwas found to be 0 F. high wax content," and if desired, this wax modi- In all of the seven tests described in the followfier may also be incorporated in similarly small ing table, 300 g. of aluminum chloride were used, amounts into paraffin wax or compositions conandin tests land 2 thealuminum chloride was taining the same to be used for various purposes, added last, whereas, in tests 3-7 the aluminum such as for coatingor' impregnating paper, etc, chloride; aromatic: compound and solvent were or for making various molded products. first mixed together and'then the ether was added Some of the condensation products of this inlast. l

Table Ether Aromatic compound Solvent (cc.) Pong goint, Test Ker,3 Tetrahis? Name G. Name G. senel lglg]; 2% 5% Di-sec.buty1 130 Naphthalene 128 500 150 4 147 0 Green viscous oil. do 130 do 128 500 150 4 78 +5 Black resin.

Di-is0propyl.. 128 i. 500 200 3 116 0 Black resin (green). .do 2 7s 500 200 v 3 43 0 Black resin, hard.

Di-sec.butyl 128 500 200 3 107 0 10 Brown resin. Di-isopropyl 100 500 200 3 120 0 0 Brown resin, hard. do Diphenyl 100 500 200 3 110 -5 Brown resin.

1 Made inert by heavy pretreatment with H2804.

Added last.

vention also are good dyes, for instance having The above table shows that by the Friedelthe property of imparting a green color to a min- Crafts condensation of lower saturated aliphatic eral oil even though the condensation product ethers with aromatic compounds, high boiling itself may be a black, hard resin. condensation products are produced which have The invention will be better understood from 0 pour-depressing properties, i. e., in 2% concentraa consideration of the following experimental tion they reduce the pour point of a waxy 111- data which are given for the sake of illustration bricating oil base stock from +30 F. to about 0 but without intending to limit the invention to F., or even lower. It should also be noted that the particular materials or operating conditions the condensationproduct of test 3 was a good used. v v 5 green dye for mineral oils.

For the sake of clearness the procedure used This application is a division of Serial No. in carrying out the first experiment will'be eX- 419,314, filed November 15, 1941. plained in detail, and for convenience and brevity, It is not intended that this invention be limited the kinds and amounts of materials, as well as to any of the specific examples which were given operating conditions used in the other tests, will merely for the sake of illustration but only by the be indicated only in the summary table in which all of the test data are given. This table also. shows the yield (weight) of product obtained and" shows the A. S. T. M. pour point data obtained appended claims in which it is intended to claim all novelty inherent in the invention as well as equivalents coming within the scope and spirit of the invention.

when the condensation products of this invention It is claimed:

1. A lubricating composition comprising a major proportion of a waxy mineral lubricating oil and a wax-modifying amount of a Friedel-Crafts condensation product of a lower saturated aliphatic ether having the general formula ROR', where R and R are alkyl groups having a total of less than carbon atoms with an aromatic compound selected from the group consisting of aromatic hydrocarbons and alkyl, hydroxy, amino, and partially hydrogenated derivatives thereof, said condensation product being nonvolatile up to 500 F. under reduced pressure, soluble in mineral oil and having wax-modifying properties.

2. A lubricant comprising a major proportion of a waxy mineral lubricating oil and about 0.5 to 10.0% of an oil-soluble, pour-depressing Friedel- Crafts condensation product of di-isopropyl ether and naphthalene, said condensation product being non-volatile up to 500? F. under reduced pressure.

3. A lubricant comprising a major proportion of waxy mineral lubricating oil and a pour-depressing amount of a Friedel-Crafts condensation product of about /2 to 2 mols of di-isopropyl ether with about 1 mol of aromatic hydrocarbon, said condensation product being non-volatile under fire and steam distillation to a temperature of at least about 500 F., soluble in mineral oil and having pour-depressing properties.

4. Composition according to claim 1 containing a condensation product of to 2 mols of the ether and 1 mol of the aromatic compound.

5. Composition according to claim 1 in which the condensation product is non-volatile up to 500 F. under reduced pressure.

6. A lubricating composition comprising a major proportion of a waxy mineral lubricating oil waxy mineral lubricating oil and a pour depressing amount of an aluminum chloride condensation product of /2 to 2 mols of di-isopropyl ether with 1 mol of naphthalene, said condensation product being non-volatile under fire and steam distillation up to'500 F. and being soluble in said waxy mineral lubricating oil.

EUGENE LIEBER. MARVIN E. THORNER. 

